Catalyst activators, processes for making same, and use thereof in catalysts and polymerization of olefins

ABSTRACT

A composition useful for activating catalysts for olefin polymerization Is provided. The composition is derived from at least: carrier; treated organoaluminoxy compound: and ionic compound having at feast one active proton.

BACKGROUND

Partially hydrolyzed aluminum alky compounds known as aluminoxanes (AO)are used for activating transition metals for olefin polymerizationactivity. One such compound, methylaluminoxane (MAO), is a frequentlychosen aluminum co-catalyst/activator in the industry. Considerableeffort has been devoted to improving the effectiveness of catalystsystems based on use of aluminoxanes of modified aluminoxanes forpolymerization of olefins. Representative patents and publications inthe field of aluminoxane usage include the following: U.S. Pat. No.5,324,800 to Welborn et al.; U.S. Pat. No. 4,752,597 to Turner; U.S.Pat. Nos. 4,980,878 and 5,041,584 to Crapo et al.; WO 96102580 toDall'occo, et al.; EP 0 277 003 and EP 0 277 004 to Turner: Hlatky,Turner, and Eckman, J. Am. Chem. Soc., 1989, 111, 2728-2729; Hlatky andUpton, Macromolecules, 1986, 29, 8019-8020. U.S. Pat. No. 6,153,157 toHlatky and Turner; U.S. Pat. No. 5,198,401 to Turner, Hlatky, andEckman; Brintzinger, et al., Angew. Chem. Int. Ed. Engl., 1995, 34,1143-1170; and the like. Despite technological advances, manyaluminoxane-based polymerization catalyst activators still lack theactivity and/or thermal stability needed for commercial applicability,require commercially unacceptably high aluminum loading, are expensive(especially MAO), and have other impediments to commercialimplementation.

Many of the limiting features surrounding the use of aluminoxanes asactivators for transition metals, for example, activity limitations—andthe need for high aluminum loading, can be addressed by the use ofstable or metastable hydroxyaluminoxanes. As compared to aluminoxanes,hydroxyaluminoxanes are generally highly active, provide reduced levelsof ash, and result in improved clarity in polymers formed from suchcatalyst compositions. One representative hydroxyaluminoxane ishydroxyisobutylaluminoxane (HO-IBAO), which can be derived from thelow-temperature hydrolysis of triisobutylaluminum (TIBA).Hydroxyaluminoxane compositions are disclosed in U.S. Pat. Nos.6,562,991, 6,555,494, 6,492,292, 6,462,212, and 6,160,145.

In contrast to aluminoxanes, which appear to act as Lewis acids toactivate transition metals, hydroxyaluminoxane species (generallyabbreviated HO-AO) comprise active protons, and appear to activatetransition metals by functioning as Brønsted acids. As used herein, anactive proton is a proton capable of metal alkyl protonation. A typicalhydroxyaluminoxane comprises a hydroxyl group bonded to at least one ofits aluminum atoms. To form hydroxyaluminoxanes, typically a sufficientamount of water is reacted with an alkyl aluminum compound underappropriate conditions, for example at low temperature in hydrocarbonsolvents, such that a compound having at least one HO-Al group isgenerated, which is capable of protonating a hydrocarbyl ligand from ad- or f-block organometallic compound to form a hydrocarbon. Therefore,polymerization catalysts derived from a hydroxyaluminoxane usuallycomprise: 1) a cation derived from a transition, lanthanide or actinidemetal compound, for example a metallocene, by loss of a leaving group,and 2) an aluminoxate anion derived by transfer of a proton from astable or metastable hydroxyaluminoxane to the leaving group. Theleaving group is usually transformed into a neutral hydrocarbon thusrendering the catalyst-forming reaction irreversible.

One feature of hydroxyaluminoxanes is that their active protons areoften thermally unstable when maintained in solution at ambienttemperatures, likely due to the loss of active protons through alkaneelimination. Thus, hydroxyaluminoxanes are frequently stored attemperatures lower than ambient temperature to maintain the activeproton concentration. Typical low temperature storage is from about −20°C. to about 0° C. In the absence of such low temperature handling, thehydroxyaluminoxane activity decreases rapidly. Low-temperature storageis commercially cost prohibitive, especially over extended periods oftime.

Thus, a need exists for hydroxyaluminoxane-type compositions that havemore thermally-robust active protons, as compared to currently availablehydroxyaluminoxanes, and that exhibit suitably high activity forcommercial olefin polymerization.

The Invention

This invention provides activator compositions derived from at least: a)carrier, b) treated organoaluminoxy compound, and c) ionic compoundhaving at least one active proton, which compositions meet theabove-described need. This invention also provides activatorcompositions derived from at least; a) carrier; b) treatedorganoaluminoxy compound; and c) N,N-dimethylaniline andpentafluorophenol in amounts such that there are at least twoequivalents of pentafluorophenol per equivalent of theN,N-dimethylaniline. This invention also provides methods of preparingcompositions comprising combining at least: a) carrier: b) treatedorganoaluminoxy compound; and c) N,N-dimethylaniline andpentafluorophenol in amounts such that there are at least twoequivalents of pentafluorophenol per equivalent of theN,N-dimethylaniline. Use of the term “at least” indicates that othercomponents may possibly be included when combining the carrier treatedorganoaluminoxy compound, and N,N-dimethylaniline and pentafluorophenolin amounts such that there are at least two equivalents ofpentafluorophenol per equivalent of the N,N-dimethylaniline, or derivinga compound therefrom. For example, a compound of this invention could bederived from, or made from a method comprising combining, (i) carrier,treated organoaluminoxy compound, and N,N-dimethylaniline andpentafluorophenol in amounts such that there are at least twoequivalents of pentafluorophenol per equivalent of thisN,N-dimethylaniline, and (ii) additional N,N-dimethylaniline. Thisinvention also provides activator compositions derived from at least: a)carrier; b) treated organoaluminoxy compound; c) N,N-dimethylaniline andd) at least two (2) equivalents (e.g., moles) of pentafluorophenol perequivalent (e.g., mole) of the N,N-dimethylaniline. Thepentafluorophenol and N,N-dimethylaniline in the prescribed 2 to 1equivalent relationship form a particularly conductive Bronsted acidicionic compound that enhances the activity of activator compositionsaccording to this invention. This invention also provides compositionsderived from at least: a) carrier; b) treated organoaluminoxy compound;and c) ionic compound having at least one active proton, which isderived from N,N-dimethylaniline and pentafluorophenol.

Activator Compositions

Activator compositions according to this invention comprise carrier,treated organoaluminoxy compound, and ionic compound having at least oneactive proton. Also provided are activator compositions derived fromcarrier, treated organoaluminoxy compound, and ionic compound having atleast one active proton combined in any order.

The combining of carrier, treated organoaluminoxy compound, and ioniccompound having at least one active proton can be conducted in an inertgas atmosphere; at a temperature from about −80° C. to about 200° C., orfrom about 0° C. to about 120° C.; the combining time can be from about1 minute to about 36 hours, or from about 10 minutes to about 24 hours.Solvent used for preparing activator composition can comprise aliphaticsolvent or aromatic solvent, either of which is inert to carrier,treated organoaluminoxy compound, and ionic compound having at least oneactive proton. Example treatments after completion of the combiningoperation include filtration of supernatant, followed by washing withinert solvent and evaporation of solvent under reduced pressure or ininert gas flow, but these treatments are not required. Resultingactivator composition can be used for polymerization in any suitablestate, including fluid, dry, or semi-dry powder, and may be used forpolymerization in the state of being suspended in inert solvent. Thecombining of carrier with treated organoaluminoxy compound can beconducted at ambient temperature and at a combining time of from about15 minutes to about 48 hours, or from about 15 minutes to about 6 hours;the resulting combination can be used as is or subsequently heated to atemperature of about 80° C. to about 120° C. Alternatively, thecombining of carrier with treated organoaluminoxy compound can beconducted at a temperature of from about 80° C. to about 120° C. at acombining time of from about 15 minutes to about 6 hours. At least aportion of resulting product is combined with ionic compound having atleast one active proton.

The amount of aluminum atom in treated alkylaluminoxane in the product,e.g., solid component, obtained by combining carrier with treatedalkylaluminoxane can be not less than about 0.1 mmol aluminum atom, ornot less than about 1 mmol aluminum atom, in 1 g of the solid componentin the dry state. When solid component obtained by combining carrierwith treated alkylaluminoxane is combined with ionic compound having atleast one active proton, the molar ratio of active proton to aluminumatom of alkylaluminoxane in the solid component can be from about 0.02to about 1, or from about 0.05 to about 0.5, or from about 0.1 to about0.3.

Activator Compositions—Carriers/Supports

Carriers useful in activator compositions according to this inventioncomprise inorganic carriers or organic carriers. A plurality of carrierscan be used as a mixture, and carriers of this invention may comprisewater, e.g., as absorbed water or in hydrate form. A carrier of thisinvention may be porous and have a micro pore volume of not less than0.1 ml/g of silica, or not less than 0.3 ml/g. A carrier of thisinvention may have a micro pore volume of about 1.6 ml/g of silica. Theaverage particle diameter of the carrier may be from about 5 micrometersto about 1000 micrometers, or from about 10 micrometers to about 500micrometers.

One silica useful in this invention is porous and has a surface area inthe range of from about 10 m²/g silica to about 700 m²/g silica, a totalpore volume in the range of from about 0.1 cc/g silica to about 4.0 cc/gsilica, and an average particle diameter in the range of from about 10micrometers to about 500 micrometers. A silica useful in this inventioncan have a surface area in the range of from about 50 m²/g to about 500m²/g, a pore volume in the range of from about 0.5 cc/g to about 3.5cc/g, and an average particle diameter in the range of from about 15micrometers to about 150 micrometers. A useful silica may have a surfacearea in the range of from about 200 m²/g to about 350 m²/g, a porevolume in the range of from about 1.0 cc/g to about 2.0 cc/g, and anaverage particle diameter in the range of from about 10 micrometers toabout 110 micrometers.

An average pore diameter of a typical porous silicon dioxide carrieruseful in this invention is in the range of from about 10 angstroms toabout 1000 angstroms, or from about 50 angstroms to about 500 angstroms,or from about 175 angstroms to about 350 angstroms. A typical content ofhydroxyl groups is from about 0.04 mmol OH/g silica to about 3.0 mmolOH/g silica, with or without the presence of free hydroxyl groups, asdetermined by the following Grignard reaction. Most of these active OHgroups react readily with benzylmagnesium chloride Grignard to producetoluene, and this reaction can be used to quantify the concentration ofactive OH groups on a particular silica. A typical content of hydroxylgroups is from about 0.10 mmol OH/g silica to about 2.0 mmol OH/gsilica, or from about 0.4 mmol OH/g silica to about 1.5 mmol OH/gsilica.

Example inorganic carriers that may be useful in this invention includeinorganic oxides, magnesium compounds, clay minerals and the like. Theinorganic oxides can comprise silica, alumina, silica-alumina, magnesia,titania, zirconia, and clays. Example inorganic oxides useful in thisinvention include, without limitation,

SiO₂, Al₂O₃, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂ and doubleoxides thereof, e.g. SiO_(2—Al) ₂O₃, SiO₂—MgO, SiO₂-iO₂, SiO₂—TiO₂—MgO.Example magnesium compounds useful in this invention include MgCl₂,MgCl(OEt) and the like. Example clay minerals useful in this inventioninclude kaolin, bentonite, kibushi clay, geyloam clay, allophane,hisingerite, pyrophylite, talc, micas, montmorillonites, vermiculite,chlorites, palygorskite, kaolinite, nacrite, dickite, halloysite and thelike.

Example organic carriers that may be useful in this invention includeacrylic polymer, styrene polymer, ethylene polymer, propylene polymerand the like. Example acrylic polymers that may be useful in thisinvention include polymers of acrylic monomers such as acrylonitrile,methyl acrylate, methyl methacrylate, methacrylonitrile and the like,and copolymers of the monomers and crosslinking polymerizable compoundshaving at least two unsaturated bonds. Example styrene polymers that maybe useful in this invention include polymers of styrene monomers such asstyrene, vinyltoluene, ethylvinylbenzene and the like, and copolymers ofthe monomers and crosslinking polymerizable compounds having at leasttwo unsaturated bonds. Example crosslinking polymerizable compoundhaving at least two unsaturated bonds include divinylbenzene,trivinylbenzene, divinyltoluene, divinylketone, diallyl phthalate,diallyl maleate, N,N′-methylenebisacrylamide, ethylene glycoldimethacrylate, polyethylene glycol dimethacrylate and the like.

Organic carrier useful in this invention has at least one polarfunctional group. Examples of suitable polar functional groups includeprimary amino group, secondary amino group, imino group, amide group,imide group, hydrazide group, amidino group, hydroxy group,hydroperoxy-group, carboxyl group, formyl group, methyloxycarbonylgroup, carbamoyl group, sulfo group, sulfino group, sulfeno group, thiolgroup, thiocarboxyl group, thioformyl group, pyrrolyl group, imidazolylgroup, piperidyl group, indazolyl group and carbazolyl group. When theorganic carrier originally has at least one polar functional group, theorganic carrier can be used as it is. One or more kinds of polarfunctional groups can also be introduced by subjecting the organiccarrier as a matrix to a suitable chemical treatment. The chemicaltreatment may be any method capable of introducing one or more polarfunctional groups into the organic carrier. For example, it may be areaction between acrylic polymer and polyalklylenepolyamine such asethylenediamine, propanediamine, diethylenetriamine,tetraethylenepentamine, dipropylenetriamine or the like. As the specificmethod of such a reaction, for example, there is a method of treating anacrylic polymer (e.g. polyacrylonitrile) in a slurry state in a mixedsolution of ethylenediamine and water at 100° C. or more, for examplefrom 120° C. to 150° C. The amount of polar functional group per unitgram in the organic carrier having a polar functional group may be from0.01 to 50 mmol/g, or from 0.1 to 20 mmol/g.

Activator Compositions—Treated Organoaluminoxy Compounds

Treated organoaluminoxy compound is derived from organoaluminoxycompound and component having at least one electron withdrawing groupand at least one active proton. Combining organoaluminoxy compound withcomponent having at least one electron withdrawing group and at leastone active proton produces treated organoaluminoxy compound.

Organoaluminoxy Compound

Organoaluminoxy compounds useful in activator compositions of thisinvention can comprise one or more organoaluminoxy compounds, includingaluminoxanes and modified aluminoxanes. Non-limiting examples includecyclic aluminoxane, for example, {—Al(R¹)—O-}_(a) and/or linearaluminoxane, for example, R¹(—Al(R¹)—O-)_(b) AlR¹ ₂ (wherein, R¹represents hydrogen or hydrocarbon group having 1 to about 20 carbonatoms, each R¹ may be the same or different; and each of “a” and “b”represents an integer of not less than 1).

Specific examples of R¹ include alkyl groups having from 1 to about 20carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, n-pentyl, neopentyl and the like. Each of “a” and “b”represent an integer of 1 to 40, or an integer of 3 to 20.

Organoaluminoxy compounds of this invention can be prepared by anysuitable method, including currently known methods. For example,alkylaluminoxane can be prepared by dissolving at least onetrialkylaluminum (e.g. trimethylaluminum, etc.) in organic solvent (e.g.toluene, aliphatic hydrocarbon, etc.). The organic solvent may compriseaqueous organic solvent. Suitable ratios of trialkylaluminum to organicsolvent include: 0.01:1 to 10:1 (mol:mol). According to another method,alkylaluminoxane can be prepared by combining at least onetrialkylaluminum (e.g. trimethylaluminum, etc.) with metal salt hydrate(e.g. copper sulfate hydrate, etc.). Suitable ratios of trialkylaluminumto metal salt hydrate include: 0.01:1 to 10:1 (mol:mol).Alkylaluminoxane may comprise trialkylaluminum and/or other materials,which are produced during preparation or otherwise.

Component Having at Least One Electron Withdrawing Group and at LeastOne Active Proton

Component having at least one electron withdrawing group and at leastone active proton comprises any component having at least one electronwithdrawing group, for example, without limitation, aromatic componentor aliphatic component having at least one electron withdrawing group,and at least one active proton.

Component having at least one electron withdrawing group and at leastone active proton can comprise conjugate base of the at least one activeproton, wherein the conjugate base comprises monodentate donorchemically bonded to at least one electron withdrawing group. Forexample, component R⁴ _(n)XH, wherein R⁴ comprises hydrocarbon grouphaving from 1 to 20 carbon atoms, X is O, S, N, or P, n is 1 when X is Oor S, and n is 2 when X is H or P, is a suitable component having atleast one electron withdrawing group and at least one active proton, R⁴_(n)X being the conjugate base of the active proton H⁺, R⁴ being a groupbearing at least one electron withdrawing group, and X being themonodentate donor. In one example, the conjugate base functions as amonodentate donor (e.g., RO⁻) and not as a multidentate donor (e.g.,RCCO⁻); for example, R⁴ _(n)XH, where R⁴ is C₆F₅ and X is O, is suitablefor use in this invention.

An electron withdrawing group comprises a substituent having a Hammettsubstituent constant σ that is positive, and examples thereof includefluoro group, chloro group, bromo group, iodo group, cyano group, nitrogroup, carbonyl group, sulfo group, phenyl group and the like.

Monodentate conjugate base of active proton comprises group capable offorming a chemical bond to organoaluminum compound; and examples thereofinclude phenoxyl group, alkoxyl group, primary amino group, secondaryamino group, imino group, amide group, imide group, thiolic group andthe like.

Component having at least one electron withdrawing group and at leastone active proton may have various and/or a plurality of electronwithdrawing groups or active protons.

Specific examples of component having at least one electron withdrawinggroup and at least one active proton include, without limitation,phenol, pentafluorophenol, 2,3,5,6-tetrafluorophenol,2,4,6-trifluorophenol, 2,3-difluorophenol, 2,4-difluorophenol,2,5-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol,3,5-difluorophenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol,2-trifluoromethylphenol, 3-trifluoromethylphenol,4-trifluoromethylphenol, pentafluorobenzyl alcohol,pentafluorothiophenol, 2,2,2-trifluoromethyl alcohol, 1H,1H-pentafluoro-propanol, 1,1,1,3,3,3-hexafluoro-2-propyl alcohol,pentachlorophenol, pentabromophenol, 2-chloro-4-fluorophenol,2-bromo-4-fluorophenol, 2-bromo-4,5-difluorophenol, tetrafluorocatechol,tetrafluorohydroquinone and the like. The foregoing examples includecomponent having at least one electron withdrawing group and at leastone active proton with the monodentate donor of its conjugate basechemically bonded to at least one electron withdrawing group. In certainembodiments, halogenated phenols, e.g., fluorinated phenols, are useful.In one embodiment, pentafluorophenol is useful.

Activator Compositions—Ionic Compound Having at Least One Active Proton

Ionic compound having at least one active proton can be derived from atleast Lewis base and component having at least one electron withdrawinggroup and at least one active proton, in one example, ionic compoundhaving at least one active proton is derived from at leastN,N-dimethylaniline and at least 2 moles of pentafluorophenol per moleof the N,N-dimethylaniline.

Lewis Base

Lewis base can comprise primary amine NH₂R², secondary amine NHR² ₂, ortertiary amine NR² ₃, or any mixture thereof, wherein R² in eachoccurrence is selected independently from hydrocarbyl group having up toabout 20 carbon atoms. Each R² can be the same as, or different from,any other R². For example, Lewis base can comprise a variety of amines,including, but not limited to, NMe₂Ph, NMe₂(CH₂Ph), NEt₂Ph, NEt₂(CH₂Ph),or Lewis base can comprise one or more long chain amines such asNMe(C_(n)H_(2n+1))(C_(m)H_(2m+1)), NMe₂(C_(n)H_(2n+1)),NEt(C_(n)H_(2n+1))(C_(m)H_(2m+1)), or NEt₂(C_(n)H_(2n+1)), wherein n andm are selected independently from an integer from about 3 to about 20.Examples of long chain amines of the formulaNMe(C_(n)H_(2n+1))(C_(m)H_(2m+1)) include, but are not limited to,compounds such as NMe(C₁₆H₃₃)₂, NMe(C₁₇H₃₅)₂, NMe(C₁₈H₃₇)₂,NMe(C₁₆H₃₃)(C₁₇H₃₅), NMe(C₁₆H₃₃)(C₁₈H₃₇), NMe(C₁₇H₃₅)(C₁₈H₃₇), and thelike. For example, NMe(C₁₆H₃₃)₂ is typically the major species in acommercial long chain amine composition that usually comprises a mixtureof several amines. Lewis base may comprise NMe₂Ph, NMe₂(CH₂Ph), NEt₂Ph,NEt₂(CH₂Ph), NMe(C₁₆H₃₃)₂. Lewis, base can also comprise phosphines.Lewis base can comprise N,N-dimethylaniline.

Catalysts for Olefin Polymerization

Activator compositions of this invention are useful in catalysis forolefin polymerization. Activator composition according to this inventionand transition metal component may each be added independently, yetsubstantially simultaneously, to monomer to catalyze polymerization.Activator composition and transition metal component may be combined toform product and at least a portion of product may be added to monomerto catalyze polymerization. The active proton ratio of activatorcomposition to transition metal atom of transition metal component maybe 0.1 to 4, or 0.5 to 2, or almost 1.

Activator composition is suitable for activating transition metalcomponent by Brønsted acidity, i.e., by protonating alkylated transitionmetal component. Activator composition is also suitable for activatingtransition metal component by Lewis acidity, i.e., by accepting at leastone electron pair from transition metal component. The amount ofactivator composition combined with transition metal component may besufficient to allow activation of transition metal componentpredominantly by Brønsted acidify; e.g., 30% or more, 70% or more, or90% or more of activation may occur due to Brønsted acidify. The amountof activator composition combined with transition metal component may besufficient to allow activation of transition metal componentsubstantially by Brønsted acidity, e.g., 95% or more, or 98% or more ofactivation may occur due to Brønsted acidity. Activator composition maybe combined with transition metal component either before combining withmonomer or while simultaneously combining with monomer. Given a knownactivator composition and a known transition metal component, oneskilled in the art can determine the amount of the activator compositionto combine with transition metal component to allow activationpredominantly or substantially by Brønsted acidity.

Catalysts for Olefin Polymerization—Transition Metal Component

Transition metal component can comprise any alkylated transition metalcomponent having olefin polymerization potential. For example, withoutlimitation, transition metal component can comprise one or moremetallocene transition metal components.

Transition metal component can comprise alkylated catalyst precursorML_(a) R_(n−a) (wherein M represents transition metal atom of the 4thGroup or Lanthanide Series of the Periodic Table of Elements (1993,IUPAC), and examples thereof include transition metals of the 4th Groupof the Periodic Table, such as titanium atom, zirconium atom and hafniumatom and transition metals of the Lanthanide Series, such as samarium; Lrepresents group having cyclopentadienyl skeleton or group having atleast one hetero atom, at least one L being group havingcyclopentadienyl skeleton, and a plurality of L may be the same ordifferent and may be crosslinked to each other; R represents hydrocarbongroup having 1 to about 20 carbon atoms; “a” represents a numeralsatisfying the expression 0<a≦n; and n represents valence of transitionmetal atom M).

In L in transition metal component, group having cyclopentadienylskeleton can comprise, for example, cyclopentadienyl group, substitutedcyclopentadienyl group or polycyclic group having cyclopentadienylskeleton. Example substituted cyclopentadienyl groups includehydrocarbon group having 1 to about 20 carbon atoms, halogenatedhydrocarbon group having 1 to about 20 carbon atoms, silyl group having1 to about 20 carbon atoms and the like. Silyl group according to thisinvention can include SiMe₃ and the like. Examples of polycyclic grouphaving cyclopentadienyl skeleton include indenyl group, fluorenyl groupand the like. Examples of hetero atom of the group having at least onehetero atom include nitrogen atom, oxygen atom, phosphorous atom, sulfuratom and the like.

Example substituted cyclopentadienyl groups includemethylcyclopentadienyl group, ethylcyclopentadienyl group,n-propylcyclopentadienyl group, n-butylcyclopentadienyl group,isopropylcyclopentadienyl group, isobutylcyclopentadienyl group,sec-butylcyclopentadienyl group, tertbutylcyclopentadienyl group,1,2-dimethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group,1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienylgroup, tetramethylcyclopentadienyl group, pentamethylcyclopentadienylgroup and the like.

Example polycyclic groups having cyclopentadienyl group include indenylgroup, 4,5,6,7-tetrahydroindenyl group, fluorenyl group and the like.

Example groups having at least one hetero atom include methylaminogroup, tert-butylamino group, benzylamino group, methoxy group,tert-butoxy group, phenoxy group, pyrrolyl group, thiomethoxy group andthe like.

One or more groups having cyclopentadienyl skeleton, or one or moregroup having cyclopentadienyl skeleton and one or more group having atleast one hetero atom, may be crosslinked with (i) alkylene group suchas ethylene, propylene and the like; (ii) substituted alkylene groupsuch as isopropylidene, diphenylmethylene and the like; or (iii)silylene group or substituted silylene group such as dimethylsilylenegroup, diphenylsilylene group, methylsilylsilylene group and the like.

R in transition metal component comprises hydrogen or hydrocarbon grouphaving 1 to about 20 carbon atoms. Examples of R include alkyl grouphaving 1 to about 20 carbon atoms such as methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, benzyl group and thelike.

Examples of transition metal component ML_(a) R_(n−a), wherein Mcomprises zirconium, include bis(cyclopentadienyl)zirconiumdimethyl,bis(methylcyclopentadienyl)zirconiumdimethyl,bis(pentamethylcyclopentadienyl)zirconiumdimethyl,bis(indenyl)zirconiumdimethyl,bis(4,5,6,7-tetrahydroindenyl)zirconiumdimethyl,bis(fluorenyl)zirconiumdimethyl, ethylenebis(indenyl)zirconiumdimethyl,dimethylsilylene(cyclopentadienylfluorenyl)zirconiumdimethyl,diphenylsilylene(indenyl)zirconiumdimethyl,cyclopentadienyldimethylaminozirconiumdimethyl,cyclopentadienylphenoxyzirconium dimethyl,dimethyl(tert-butylamino)(tetramethylcyclopentadienyl)silanezirconiumdimethyl,isopropylidene(cyclopentadienyl)3-tert-butyl-5-methyl-2-phenoxy)zirconiumdimethyl,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)zirconiumdimethyl and the like.

Additional exemplary transition metal component ML_(a) R_(n−a) includecomponents wherein zirconium is replaced with titanium or hafnium in theabove zirconium components.

Other alkylated catalyst precursors which may be useful in thisinvention are: rac-dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconiumdimethyl (M1); rac-dimethylsilylbis(2-methyl-1-indenyl) zirconiumdimethyl (M2); rac-dimethylsilylbis(2-methyl-4,5-benzoindenyl) zirconiumdimethyl (M3); ethylenebis(tetrahydroindenyl)-zirconium dimethyl (M4),and ethylenebis(indenyl) zirconium dimethyl (M5). Alkylated catalystprecursor can be generated in-situ through reaction of alkylation agentwith the halogenated version of the catalyst precursor. For example,

bis(cyclopentadienyl)zirconium dichloride can be treated withtriisobutylaluminum (TIBA) and than combined with activator composition.

Polymerization Using Activator Compositions of the Invention

When using activator compositions of the present invention inpolymerization, any olefin or dioelfln having 2 to 20 carbon atoms canbe used as a monomer for polymerization. Specific examples thereofinclude ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1,octene-1, nonene-1, decene-1, hexadecene-1,eicocene-1,4-methylpentene-1,5-methyl-2-pentene-1, vinylcyclohexane,styrene, dicyclopentadiene, norbornene, 5-ethylidene-2-norbornene andthe like, but are not limited thereto, in the present invention,copolymerization can be conducted using two or more monomers,simultaneously. Specific examples of the monomers constituting thecopolymer include ethylene/an α olefin such as ethylene/propylene,ethylene/butene-1, ethylene/hexene-1, ethylene/propylene/butene-1,ethylene/propylene/5-ethylidene-2-norbornene and the like,propylene/butene-1, and the like, but are not limited thereto.

The polymerization method is not limited, and both liquid phasepolymerization method and gas phase polymerization method can be used.Examples of solvent used for liquid phase polymerization includealiphatic hydrocarbons such as butane, pentane, heptane, octane and thelike; aromatic hydrocarbons such as benzene, toluene and the like; andhydrocarbon halides such as methylene chloride and the like. It is alsopossible to use at least a portion of the olefin to be polymerized as asolvent. The polymerization can be conducted in a batch-wise,semibatch-wise or continuous manner, and polymerization may be conductedin two or more stages which differ in reaction conditions. Thepolymerization temperature can be from about 50° C. to about 200° C., orfrom 0° C. to about 100° C. The polymerization pressure can be fromatmospheric pressure to about 100 kg/cm², or from atmospheric pressureto about 50 kg/cm². Appropriate polymerization time can be determined bymeans known to those skilled in the art according to the desired olefinpolymer and reaction apparatus, and is typically within the range fromabout 1 minute to about 20 hours. In the present invention, a chaintransfer agent such as hydrogen may be added to adjust the molecularweight of olefin polymer to be obtained in polymerization.

Organoaluminum compound can be added during polymerization to removeimpurities, such as water. Organoaluminum compound useful herein cancomprise a variety of organoaluminum compounds, including at least onecurrently known organoaluminum compound, for example, organoaluminumcompound R³ _(c) AlY_(3−c) (wherein R³ represents a hydrocarbon grouphaving 1 to about 20 carbon atoms; Y represents hydrogen atom and/orhalogen atoms; and “c” represents an integer of 0 to 3). Specificexamples of R³ include methyl group, ethyl group, n-propyl group,n-butyl group, isobutyl group, n-hexyl group and the like. Specificexamples of the halogen atom for Y include fluorine atom, chlorine atom,bromine atom and iodine atom. Specific examples of the organoaluminumcompound R³ _(c) AlY_(3−c) include trialkylaluminums such astrimethylaluminum, triethylaluminum, tri-n-propylaluminum,trisobutylaluminum, tri-n-hexylaluminum and the like; dialkylaluminumchloride such as dimethylaluminum chloride, diethylaluminum chloride,di-n-propylaluminum chloride, diisobutylaluminum chloride,di-n-hexylaluminum chloride and the like; alkylaluminum dichlorides suchas methylaluminumdichloride, ethylaluminum dichloride, n-propylaluminumdichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride andthe like; and dialkylaluminum hydrides such as dimethylaluminum hydride,diethylaluminum hydride, di-n-propylaluminum hydride, diisobutylaluminumhydride, di-n-hexylaluminum hydride and the like.

EXAMPLES Preparation of Ionic Compound

In a drybox, 2.00 g (0.0108 mol) of C₆F₅OH (pentafluorophenol) was mixedwith 0.657 g (0.00540 mol) of NMe₂Ph (N, N-dimethylaniline) in a vial.After a few hours the slurry mixture solidified to form a crystallinesolid. The resulting solid was analyzed by ¹H NMR and It showed that thesolid had a composition of two moles of pentafluorophenol per mole of N,N-dimethylaniline (structure shown below).

Conductivity Test of IBA

Table 1 lists the conductivity of several samples.

TABLE 1 Conductivity Results Obtained in CH₃CN Solution at RoomTemperature Sample No. 1 2 3 4 Sample C₆F₅OH PhNMe₂ C₆F₅OH + C₆F₅OH +only only PhNMe_(2 (1:1)) 0.5 PhNMe_(2 (2:1)) Concentration 1.09 1.09¹1.09 1.09 (mmol/g) of phenol Conductivity 314 92.9 2,217 2,049 (uS/cm)¹concentration of amine (since no phenol included)

The increases in conductivity of samples 3 and 4 (over that of samples 1and 2) confirms the formation of ionic species. In sample 3, the excessamine adds to the conductivity, but not substantially. The excess amountof amine in the 1:1 charged sample (sample 3) does not formsignificantly more ionic compound. Therefore, a 1:1 charge of the twocomponents only forms 0.5 equivalent of the ionic species with 0.5equivalent of excess amine.

In these examples, IBA was prepared according to the method describedabove. Also the amount of IBA:Al ratio was half of C6F5OH:Al becausethere are two moles of C6F5OH in IBA. One of the examples used IBA only(C6F5OH:Amine=2.1) (see entry 4); and some of the examples used amixture of IBA and Amine (C6F5OH:Amine=2:2) (see entries 2 and 3).Conductivity data indicates that the species with C6F5OH:Amine=2:2 was amixture of IBA and amine, not another new species. Also, when thereaction was done in isohexane, IBA was the solid precipitate and theexcess amine was washed away during isolation.

Comparative Example (Entry 1 in Table 2)

Silica was first calcined at the temperature indicated in Table 2 for 4hours (h) and cooled to room temperature. Aluminoxane in toluene wasadded to the slurry of silica and toluene slowly at room temperature;the resulting slurry was heated and then stirred for 3 h at 100° C. Thesolid support was then filtered, washed three times with isohexane anddried under vacuum. IBA or IBA and amine N, N-dimethylaniline mixturewas dissolved in toluene and added to the support/toluene slurry. Thereaction was shaken for 2˜4 h to form the supported activator.Metallocene and toluene were added to the solid support and the reactionwas shaken overnight. The catalyst was filtered, washed three times withtoluene and three times with isohexane, and then dried under vacuum.(see data in Table 2, Attachment 1)

Examples of Invention (Entries 2 through 4in Table 2)

Silica was first calcined at the temperature indicated in Table 2 for 4h and cooled to room temperature. An amount of C₆F₅OH as shown in Table2 was dissolved in toluene and added to aluminoxane in toluene at roomtemperature. The reaction was stirred for a few hours at roomtemperature or heated and stirred for 1 h at 85° C. The modifiedaluminoxane in toluene was added to the slurry of silica and tolueneslowly at room temperature; the resulting slurry was heated and thenstirred for 3 h at 100° C. The solid support was then filtered, washedthree times with isohexane and dried under vacuum. IBA or IBA and amineN, N-dimethylaniline mixture was dissolved in toluene and added to thesupport/toluene slurry. The reaction was shaken for 2-4 h to form thesupported activator. Metallocene and toluene were added to the supportedactivator and the reaction was shaken overnight. The catalyst wasfiltered, washed three times with toluene and three times withisohexane, and then dried under vacuum. (see data in Table 2, Attachment1)

Polymerization Test

A 4 L reactor was dried by heating at 100° C. for 15 minutes minimumunder low pressure nitrogen flow. After cooling to ambient, the reactorwas pressurized with isobutane and vented three times to removenitrogen. Isobutane (1800 ml) was charged into the reactor while adding40 ml of dried 1-hexene and 2 ml of 10% TIBA scavenger, such asorganoaluminum compound as described herein. The reactor agitator wasset at 800 rpm. After flushing the charging line with 200 ml ofisobutane, the reactor was charged with ethylene up to 320 psi forsupported M5 while at the same time bringing the temperature of thereactor up to 80° C. Then, 30-100 mg of solid catalyst was slurried in 2ml of hexane in the glovebox and then injected into the reactor. Thereaction pressure was maintained at 320 psi and the polymerization wascarried out for 1 hour at 80° C. The reaction was stopped by venting offthe ethylene and isobutane. The polymer was isolated, dried, andweighed. The polymerization productivity and activity of each catalystwas calculated and is listed in Table 2, Attachment 1.

The supported M5 catalysts from pretreated EAO/silica gave much betterproductivity and activity than that from the non-treated EAO/silica.Even when the Zr loading was very low, as in Entry 4, the catalyst stillshowed high productivity and great activity. For supported M1 catalyst(data not shown), the pretreated sample had similar activity as thenon-pretreated sample.

While the present invention has been described in terms of one or morepreferred embodiments, it is to be understood that other modificationsmay be made without departing from the scope of the invention, which isset forth in the claims below.

Attachment 1

TABLE 2 Silica/ Entry Calcination IBA Amine Al Zr Productivity Activity# Temperarure RAO (mol % Al) (mol % Al) Mtn wt % wt % (g/g cat/h) (Kg/gZr/h) 1 G952/600° C. EAO 20 20 M5 8.09 0.418 3,300 789 2 ES70/600° C. 5% C₆F₅OH-EAO 20 20 M5 6.89 0.55 8,000 1,450 3 ES70/600° C. 10%C₆F₅OH-EAO 20 20 M5 7.32 0.57 6,200 1,080 4 ES70/600° C. 10% C₆F₅OH-EAO20 0 M5 7.11 0.20 5,600 2,820

1. A composition derived from at least: a) carrier; b) treatedorganoaluminoxy compound, which is derived from at least organoaluminoxycompound and component having at least one electron withdrawing groupand at least one active proton; and c) ionic compound having at leastone active proton.
 2. The composition of claim 1, wherein the carriercomprises inorganic oxide.
 3. The composition of claim 2, wherein theinorganic oxide has a micro pore volume of not less than about 0.3 ml/gand an average particle diameter of about 10 micrometers to about 500micrometers.
 4. The composition of claim 2 wherein the inorganic oxidecomprises silica, alumina, silica-alumina, magnesia, titania, zirconia,or clays.
 5. The composition of claim 1 wherein the organoaluminoxycompound comprises an alkylaluminoxane.
 6. The composition of claim 5wherein the alkylaluminoxane comprises methylaluminoxane,ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane,n-butylaluminoxane, iso-butylaluminoxane, sec-butylaluminoxane,n-pentylaluminoxane, n-hexylaluminoxane, n-heptylaluminoxane, orn-octylaluminoxane.
 7. The composition of claim 1 wherein the componenthaving at least one electron withdrawing group and at least one activeproton comprises pentafluorophenol, 2,3,5,6-tetrafluorophenol,2,4,6-trifluorophenol, 2,3-difluorophenol, 2,4-difluorophenol,2,5-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol,3,5-difluorophenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol,2-trifluoromethylphenol, 3-trifluoromethylphenol,4-trifluoromethylphenol, pentafluorobenzyl alcohol,pentafluorothiophenol, 2,2,2-trifluoroethyl alcohol, 1H,1H-pentafluoro-propanol, 1,1,1,3,3,3-hexafluoro-2-propyl alcohol,pentachlorophenol, pentabromophenol, 2-chloro-4-fluorophenol,2-bromo-4-fluorophenol, 2-bromo-4,5-difluorophenol, tetrafluorocatechol,or tetrafluorohydroquinone.
 8. The composition of claim 1, wherein theionic compound having at least one active proton is derived from atleast Lewis base and a portion of the component having at least oneelectron withdrawing group and at least one active proton.
 9. Thecomposition of claim 8 wherein the Lewis base comprises at least one NR²₃, wherein each R² is a hydrocarbyl group having up to about 20 carbonatoms and each R² can be the same as, or different from, any other R².10. The composition of claim 8, wherein the Lewis base comprises NMe₂Ph,NMe₂(CH₂Ph), NEt₂Ph, NEt₂(CH₂Ph), NMe(C_(n)H_(2n+1))(C_(m)H_(2m+)),NMe₂(C_(n)H_(2n+1)), NEt(C_(n)H_(2n+1))(C_(m)H_(2m+1)), orNEt₂(C_(n)H_(2n+1)) and wherein n and m are independently an integerfrom 3 to
 20. 11. The composition of claim 1, wherein the composition issuitable for activating an alkylated transition metal component byprotonation.
 12. A composition derived from at least: a) carrier; b)treated organoaluminoxy compound, which is derived from at leastorganoaluminoxy compound and component having at least one electronwithdrawing group and at least one active proton; and c) N,N-dimethylaniline and pentafluorophenol in amounts such that there areat least 2 moles of pentafluorophenol per mole of theN,N-dimethylaniline.
 13. A catalyst for olefin polymerization, whereinthe catalyst comprises the composition of claim 1 and alkylatedtransition metal component.
 14. A method of preparing a compositioncomprising combining at least: a) a carrier; b) a treatedorganoaluminoxy compound, which is prepared by combining at least anorganoaluminoxy compound and a component having at least one electronwithdrawing group and at least one active proton; and c) an ioniccompound having at least one active proton.
 15. The method of claim 14wherein the carrier comprises inorganic oxide.
 16. The method of claim14 wherein the carrier, the treated organoaluminoxy compound, and theionic compound having at least one active proton are combined in amountssufficient and under conditions sufficient such that the composition issuitable for activating alkylated transition metal component byprotonation.
 17. A method of preparing a catalyst for olefinpolymerization, comprising combining alkylated transition metalcomponent with composition derived from at least carrier; treatedorganoaluminoxy compound, which is derived from at least organoaluminoxycompound and component having at least one electron withdrawing groupand at least one active proton; and ionic compound having at least oneactive proton.
 18. A method of polymerizing monomer comprising combiningthe catalyst of claim 13 and monomer.
 19. A method of polymerizingmonomer comprising combining the composition of claim 1, alkylatedtransition metal component, and monomer.
 20. A composition derived fromat least: a) carrier; b) treated organoaluminoxy compound, which isderived from at least organoaluminoxy compound and component having atleast one electron withdrawing group and at least one active proton; andc) ionic compound having at least one active proton, which is derivedfrom N,N-dimethylaniline and pentafluorophenol.
 21. A method ofpreparing a composition comprising combining at least: a) carrier; b)treated organoaluminoxy compound, which is derived from at leastorganoaluminoxy compound and component having at least one electronwithdrawing group and at least one active proton; and c) ionic compoundhaving at least one active proton, which is derived fromN,N-dimethylaniline and pentafluorophenol.